CN110691833B - Non-polar vinylic compositions with triallyl phosphate for encapsulating films - Google Patents

Non-polar vinylic compositions with triallyl phosphate for encapsulating films Download PDF

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CN110691833B
CN110691833B CN201780091300.7A CN201780091300A CN110691833B CN 110691833 B CN110691833 B CN 110691833B CN 201780091300 A CN201780091300 A CN 201780091300A CN 110691833 B CN110691833 B CN 110691833B
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ethylene
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CN110691833A (en
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何超
B·I·乔杜里
B·海伯斯伯格
杨红
马伟明
李宇岩
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Dow Global Technologies LLC
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    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
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    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
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    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08L2203/16—Applications used for films
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Abstract

An encapsulating film made from a composition comprising: (A) a non-polar ethylenic polymer having a density of 0.850g/cc to 0.890 g/cc; (B) an organic peroxide; (C) a silane coupling agent; and (D) an adjuvant comprising triallyl phosphate.

Description

Non-polar vinylic compositions with triallyl phosphate for encapsulating films
Technical Field
The present disclosure relates to non-polar ethylenic polymer compositions for encapsulating films. In one aspect, the present disclosure relates to non-polar ethylenic polymer compositions having high volume resistivity, while in another aspect, the present disclosure relates to encapsulating films comprising non-polar ethylenic polymer compositions and electronic devices comprising the encapsulating films.
Background
Over the past decade, global demand for alternative energy has caused a substantial increase in solar panel and Photovoltaic (PV) module production. Solar cells (also referred to as PV cells) that convert solar energy into electrical energy are fragile and must be surrounded by a durable encapsulant film. The two primary functions of the encapsulant film are (1) to bond the solar cells to the glass cover and back sheets and (2) to protect the PV module from environmental stresses (e.g., moisture, temperature, shock, vibration, electrical isolation, etc.).
For use as an encapsulant film, the film must exhibit (a) good lamination properties, (b) strong adhesion to glass, PV cells and back sheets, (c) good electrical insulation (low leakage current, high volume resistivity), (d) good light transmission, (e) low water vapor permeability and moisture absorption, (f) good creep resistance, (g) stability in UV exposure, and (h) good weatherability. Current encapsulation films are mainly made of Ethylene Vinyl Acetate (EVA) because EVA shows a good balance of (a) - (h). EVA is a type of ethylene/unsaturated carboxylic acid ester copolymer in which the unsaturated carboxylic acid ester comonomer is a vinyl carboxylate ester. Because EVA is readily used to form encapsulation films, a number of additive packages have been developed to enhance one or more of (a) - (h).
Non-polar polyolefins such as ethylene-based elastomers other than ethylene/unsaturated carboxylic acid ester copolymers have been used in the manufacture of encapsulation films, but still require organic peroxides and coupling agents (typically silane coupling agents) in order to adequately bond to glass. A crosslinking assistant is generally used together with the nonpolar polyolefin-based encapsulating film in order to obtain sufficient glass adhesion. However, many conventional crosslinkers are problematic because they reduce the volume resistivity of the encapsulating film. Accordingly, the art recognizes the need for a crosslinking aid that provides sufficient glass adhesion and improves the volume resistivity of the encapsulation film.
Disclosure of Invention
The present disclosure provides an encapsulation film. An encapsulating film comprises a composition comprising (A) a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890 g/cc; (B) an organic peroxide; (C) a silane coupling agent; and (D) an adjuvant comprising triallyl phosphate.
In another embodiment, the present disclosure provides an electronic device module. An electronic device module comprises an electronic device and at least one film comprised of a crosslinked polymer composition that is the reaction product of a composition comprising: (A) a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890 g/cc; (B) an organic peroxide; (C) a silane coupling agent; and (D) an adjuvant comprising triallyl phosphate.
Drawings
Fig. 1 is an exploded perspective view of an exemplary photovoltaic module.
Definition and testing method
Any reference to the periodic Table of elements is the periodic Table of elements published by CRC Press, Inc., 1990 and 1991. Reference to a set of elements in this table is made to each set by a new symbol number.
For purposes of united states patent practice, the contents of any referenced patent, patent application, or publication are incorporated by reference in their entirety (or the equivalent us version thereof is so incorporated by reference), especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.
The numerical ranges disclosed herein include all values from and including the lower value and the upper value. For ranges containing an explicit value (e.g. 1 or 2 or 3 to 5 or 6 or 7) any subrange between any two explicit values is included (e.g. 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.).
Unless stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure.
Unless stated to the contrary, all test methods were current test methods as of the filing date of this disclosure.
"blend," "polymer blend," and similar terms mean a composition of two or more polymers. Such blends may or may not be miscible. Such blends may or may not be phase separated. Such blends may or may not contain one or more domain configurations, as determined by transmission electron spectroscopy, light scattering, x-ray scattering, and any other method for measuring and/or identifying domain configurations. The blend is not a laminate, but one or more layers of the laminate may contain the blend.
As used herein, "composition" includes materials comprising the composition as well as mixtures of reaction products and decomposition products formed from materials having the composition.
The terms "comprising," "including," "having," and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant or compound, whether polymeric or otherwise. In contrast, the term "consisting essentially of … …" excludes any other components, steps, or procedures from any subsequently recited range except for components, steps, or procedures not essential to operability. The term "consisting of … …" excludes any component, step or procedure not specifically listed. Unless otherwise indicated, the term "or" refers to the listed members individually as well as in any combination. The use of the singular includes the plural and vice versa.
Crosslinking or curing was tested using a rotor-free vulkameter (moving die rheometer). The rotorless vulanizer (MDR) was charged with 5 grams of each sample. The MDR was run for 25 minutes and the samples were given time versus torque curves at given intervals. The MDR was run at 130 ℃ and 150 ℃. 130 ℃ represents the maximum film manufacturing temperature. 150 ℃ represents the module lamination temperature. The maximum torque applied by the MDR during the 25 minute test interval (MH) is reported in units of dNm. MH generally corresponds to the torque applied at 25 minutes. The torque reaches X% MH (t) x ) The time spent is reported in minutes. t is t x Is a standardized measure for understanding the cure kinetics of each resin. Up to 90% MH (T) 90 ) Time of (d) is reported in minutes.
Density is measured according to ASTM D792. The results are in grams (g)/cubic centimeter (g/cc or g/cm) 3 ) To be recorded.
"direct contact" refers to a layer configuration whereby a first layer is positioned immediately adjacent to a second layer, and there are no intervening layers or no intervening structures between the first and second layers.
An "ethylene-based polymer" is a polymer that contains more than 50% by weight polymerized ethylene monomer (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" are used interchangeably. Non-limiting examples of ethylene-based polymers (polyethylenes) include Low Density Polyethylene (LDPE) and linear polyethylenes. Non-limiting examples of linear polyethylenes include Linear Low Density Polyethylene (LLDPE), Ultra Low Density Polyethylene (ULDPE), Very Low Density Polyethylene (VLDPE), multicomponent ethylene copolymers (EPE), ethylene/alpha-olefin multi-block copolymers (also known as Olefin Block Copolymers (OBC)), single site catalyzed linear low density polyethylene (m-LLDPE), substantially linear or linear plastomers/elastomers, Medium Density Polyethylene (MDPE), and High Density Polyethylene (HDPE). In general, polyethylene can be produced in a gas phase fluidized bed reactor, a liquid phase slurry process reactor, or a liquid phase solution process reactor using a heterogeneous catalyst system, such as a Ziegler-Natta catalyst (Ziegler-Natta catalyst), a homogeneous catalyst system comprising a group 4 transition metal and a ligand structure such as a metallocene, a non-metallocene-centered heteroaryl, a heterovalent aryloxyether, a phosphinimine, and others. Heterogeneous and/or homogeneous catalyst combinations may also be used in single reactor or dual reactor configurations.
Glass bond strength (maximum glass bond strength and average glass bond strength of 1 "to 2") was measured by 180 ° peel test. The backsheet and film layers of each of the laminated samples (e.g., comparative example formulation and inventive example formulation) were cut to separate each laminated sample into three 1 inch wide strip samples, and the strip samples remained bonded to the glass layer. 180 peel tests were performed on an Instron TM 5565 under controlled ambient conditions. Initial glass adhesion was tested and the results are reported in newtons/cm. Three samples were tested to obtain the average glass bond strength of each sample.
Glass transition temperature (Tg) is measured according to ASTM D7028.
As used herein, "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. Thus, the generic term interpolymer includes copolymers (employed to refer to polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers.
Melt Index (MI) is measured according to ASTM D1238 at 190 ℃, 2.16kg and is reported in grams per 10 minutes (g/10 min).
Melting points were measured according to ASTM D3418.
"non-polar ethylene-based polymer" and similar terms refer to ethylene-based polymers that do not have permanent dipoles, i.e., polymers that do not have a positive and negative terminal and that do not have heteroatoms and functional groups. "functional group" and like terms refer to a moiety or group of atoms responsible for causing a characteristic reaction of a particular compound. Non-limiting examples of functional groups include heteroatom-containing moieties, oxygen-containing moieties (e.g., alcohol, aldehyde, ester, ether, ketone, and peroxy groups), and nitrogen-containing moieties (e.g., amide, amine, azo, imide, imine, nitrate, nitrile, and nitrite groups). As defined above, a "heteroatom" is an atom other than carbon or hydrogen.
"photovoltaic cell," "PV cell," and like terms mean a structure containing one or more photovoltaic effect materials of any of several inorganic or organic types known in the art and from the teachings of prior art photovoltaic modules. For example, common photovoltaic effect materials include one or more of known photovoltaic effect materials including, but not limited to, crystalline silicon, polycrystalline silicon, amorphous silicon, copper indium gallium (di) selenide (CIGS), Copper Indium Selenide (CIS), cadmium telluride, gallium arsenide, dye sensitized materials, and organic solar cell materials. As shown in fig. 1, PV cells are typically used in a laminate structure and have at least one photo-reactive surface that converts incident light into electrical current. Photovoltaic cells are well known to practitioners in this field and are typically packaged into photovoltaic modules that protect the cell and permit the cell to be used in its various application environments, typically in outdoor applications. PV cells can be flexible or rigid in nature and include photovoltaic effect materials and any protective coating surface materials applied in PV cell production as well as appropriate wiring and electronic drive circuitry.
"photovoltaic module," "PV module," and similar terms refer to structures that include PV cells. The PV module can also include a cover sheet, a front encapsulant film, a back encapsulant film, and a back sheet, with the PV cells sandwiched between the front and back encapsulant films.
As used herein, "polymer" refers to a polymer compound prepared by polymerizing monomers of the same or different types. Thus, the generic term polymer encompasses the term homopolymer (used to refer to polymers prepared from only one type of monomer, and it is understood that trace amounts of impurities may be incorporated into the polymer structure) as well as the term interpolymer as previously defined. Trace impurities (e.g., catalyst residues) can be incorporated into and/or within the polymer.
Volume resistivity was measured according to the Dow method based on ASTM D257. Measurements were made using a Keithley 6517B electrometer in combination with a Keithley 8009 test fixture. The Keithley model 8009 test chamber was located inside a forced draft oven and was capable of operating at high temperatures (oven max. temperature 80 ℃). The leakage current was read directly from the instrument and the volume resistivity was calculated using the following equation:
Figure BDA0002290817690000061
where ρ is the volume resistivity (ohm. cm), V is the applied voltage (volts), A is the electrode contact area (cm) 2 ) I is the leakage current (amperes) and t is the average thickness of the sample. To obtain the average thickness of the samples, the thickness of each sample was measured before the test, and five points of the sample were measured to obtain the average thickness. The volume resistivity test was performed at 1000 volts at 60 ℃. Two compression molded films were tested to obtain an average value.
Detailed Description
In one embodiment, the present disclosure provides an encapsulating film comprising a composition comprising (a) a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890 g/cc; (B) an organic peroxide; (C) a silane coupling agent; and (D) an adjuvant comprising triallyl phosphate.
Composition comprising a metal oxide and a metal oxide
A composition comprising (a) a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890 g/cc; (B) an organic peroxide; (C) a silane coupling agent; and (D) an adjuvant comprising triallyl phosphate, the composition being for forming an encapsulation film.
(A) Non-polar ethylene polymers
The composition comprises a non-polar ethylenic polymer.
In one embodiment, the non-polar ethylenic polymer has a density of 0.850g/cc, or 0.855g/cc, or 0.860g/cc, or 0.865g/cc, or 0.870g/cc to 0.875g/cc, or 0.880g/cc, or 0.885g/cc, or 0.890g/cc, or 0.900 g/cc.
In one embodiment, the non-polar ethylenic polymer has a melting point of 40 ℃ or 45 ℃ or 50 ℃ or 55 ℃ to 60 ℃ or 65 ℃ or 70 ℃ or 80 ℃ or 90 ℃ or 95 ℃ or 100 ℃ or 110 ℃ or 120 ℃ or 125 ℃.
In one embodiment, the non-polar ethylenic polymer has a glass transition temperature (Tg) of-35 deg.C or-40 deg.C or-45 deg.C or-50 deg.C to-80 deg.C or-85 deg.C or-90 deg.C or-95 deg.C or-100 deg.C.
In one embodiment, the non-polar ethylenic polymer has a Melt Index (MI) of 2g/10min or 5g/10min or 10g/10min or 12g/10min to 30g/10min or 35g/10min or 40g/10min or 45g/10min or 50g/10 min.
In one embodiment, the non-polar ethylene-based polymer is an ethylene/a-olefin interpolymer. The ethylene/a-olefin interpolymer may be a random interpolymer or a block interpolymer.
An α -olefin is a hydrocarbon molecule composed of hydrocarbon molecules comprising: (i) only one ethylenic unsaturation, such unsaturation being located between a first carbon atom and a second carbon atom, and (ii) at least 3 carbon atoms or from 3 to 20 carbon atoms, or in some cases from 4 to 10 carbon atoms, and in other cases from 4 to 8 carbon atoms. Non-limiting examples of suitable alpha-olefins for making the copolymer include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene and mixtures of two or more of these monomers.
Non-limiting examples of suitable ethylene/α -olefin interpolymers include ethylene/propylene, ethylene/butene, ethylene/1-hexene, ethylene/1-octene, ethylene/propylene/butene, and ethylene/butene/1-octene interpolymers. In one embodiment, the ethylene/a-olefin interpolymer is a copolymer. Non-limiting examples of suitable ethylene/α -olefin copolymers include ethylene/propylene copolymers, ethylene/butene copolymers, ethylene/1-hexene copolymers, and ethylene/1-octene copolymers.
In one embodiment, the non-polar ethylene-based polymer is an ethylene/a-olefin interpolymer. The ethylene/α -olefin interpolymer has one, some, or all of the following properties:
(i) a density of 0.850g/cc or 0.855g/cc or 0.860g/cc or 0.865g/cc or 0.870g/cc to 0.875g/cc or 0.880g/cc or 0.885g/cc or 0.890g/cc or 0.900 g/cc;
(ii) the melt index is 2g/10min or 5g/10min or 10g/10min or 12g/10min to 30g/10min or 35g/10min or 40g/10min or 45g/10min or 50g/10 min; and/or
(iii) The melting point (Tm) is from 40 ℃ or 45 ℃ or 50 ℃ or 55 ℃ to 60 ℃ or 65 ℃ or 70 ℃ or 80 ℃ or 90 ℃ or 95 ℃ or 100 ℃ or 110 ℃ or 120 ℃ or 125 ℃.
In one embodiment, the ethylene/a-olefin interpolymer has at least 2 or all 3 of properties (i) - (iii).
In one embodiment, the non-polar ethylenic polymer is present in the composition in an amount of 50 weight percent (wt%), or 80 wt%, or 95 wt% to 98.5 wt%, or 98.75 wt%, or 99.0 wt%, or 99.5 wt%, or less than 100 wt%, based on the total weight of the composition.
Blends of non-polar ethylene-based polymers may also be used, and the non-polar ethylene-based polymer may be blended or diluted with one or more other polymers to the extent that the polymers (i) are miscible with each other, (ii) the other polymers have little, if any, effect on the desired properties of the non-polar ethylene-based polymer, and (iii) the non-polar ethylene-based polymer comprises from 70 wt% or 75 wt% or 80 wt% or 85 wt% or 90 wt% to 95 wt% or 98 wt% or 99 wt% or less than 100 wt% of the blend.
Non-limiting examples of suitable commercially available nonpolar vinyl polymers include ENGAGE resins from Dow Chemical, EXACT resins from EMCC, and LUCENE resins from LG Chemical.
(B) Organic peroxides
The composition includes an organic peroxide. Non-limiting examples of suitable organic peroxides include dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl perbenzoate, di (t-butyl) peroxide, cumene hydroperoxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 2, -5-dimethyl-2, 5-di (t-butylperoxy) hexane, t-butyl hydroperoxide, isopropyl percarbonate, α' -bis (t-butylperoxy) diisopropylbenzene, t-butylperoxy-2-ethylhexyl-monocarbonate, 1-bis (t-butylperoxy) -3,5, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-dihydroxyperoxide, t-butylcumyl peroxide, α, α' -bis (t-butylperoxy) -p-diisopropylbenzene, and the like.
Non-limiting examples of suitable commercially available organic peroxides include trigonox (r) from akzo nobel (akzo nobel) and luperox (r) from ARKEMA (ARKEMA).
In one embodiment, the organic peroxide is present in the reaction composition in an amount of from 0.1 wt%, or 0.5 wt%, or 0.75 wt% to 1.5 wt%, or 2 wt%, or 3 wt%, or 5 wt%, based on the total weight of the reaction composition.
(C) Silane coupling agent
The composition includes a silane coupling agent. In one embodiment, the silane coupling agent contains at least one alkoxy group. Non-limiting examples of suitable silane coupling agents include gamma-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris- (beta-methoxy) silane, gamma-methacryloxypropyltrimethoxysilane, beta- (3, 4-ethoxy-cyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, and 3- (trimethoxysilyl) propyl methacrylate.
In one embodiment, the silane coupling agent is vinyltrimethoxysilane or 3- (trimethoxysilyl) propyl methacrylate.
In one embodiment, the silane coupling agent is present in an amount of 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.2 wt% to 0.3 wt%, or 0.5 wt%, or 1 wt%, or 2 wt%, based on the total weight of the reaction composition.
(D) Auxiliary agent
The composition comprises an adjuvant comprising triallyl phosphate. The triallyl phosphate has structure I:
Figure BDA0002290817690000091
in one embodiment, the adjuvant is present in an amount of 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.15 wt%, or 0.2 wt% to 0.4 wt%, or 0.6 wt%, or 0.8 wt%, or 1.0 wt%, or 1.3 wt%, or 1.5 wt%, based on the total weight of the composition.
In one embodiment, the adjuvant consists solely of triallyl phosphate. In the described embodiments, the triallyl phosphate is present in an amount of 0.01 wt%, or 0.05 wt%, or 0.1 wt%, or 0.15 wt%, or 0.2 wt% to 0.4 wt%, or 0.6 wt%, or 0.8 wt%, or 1.0 wt%, or 1.3 wt%, or 1.5 wt%, based on the total weight of the composition.
In one embodiment, the adjuvant comprises a blend of triallyl phosphate and at least one other compound. Exemplary compounds that may be blended with triallyl phosphate include triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC). In one embodiment, the coagent comprises a blend of triallyl phosphate and at least one of (i) TAC and (ii) TAIC. In the blend, the triallyl phosphate comprises from more than 0 wt%, or 1 wt%, or 20 wt%, or 50 wt% to 99 wt%, or 99.5 wt%, or to less than 100 wt% of the blend. For example, in embodiments where the adjunct comprises a blend of triallyl phosphate and at least one of (i) TAC and (ii) TAIC, the triallyl phosphate comprises more than 0 wt% or 0.01 wt% or 0.05 wt% or 0.1 wt% or 0.15 wt% or 0.2 wt% or 0.4 wt% or 0.6 wt% or 0.8 wt% or 1 wt% or 1.3 wt% or 1.5 wt% or 5 wt% or 10 wt% or 15 wt% or 20 wt% or 50 wt% to 99 wt% or 99.5 wt% or less than 100 wt% by weight of the blend, and at least one of (i) TAC and (ii) TAIC comprises more than 0 wt% or 0.5 wt% or 1 wt% to 50 wt% or 80 wt% or 99 wt% based on the total weight of the blend.
(E) Optional additives
In one embodiment, the composition includes one or more optional additives. Non-limiting examples of suitable additives include antioxidants, antiblock agents, stabilizers, colorants, Ultraviolet (UV) absorbers or stabilizers, flame retardants, compatibilizers, fillers, and processing aids.
The optional additives are present in an amount of more than zero or 0.01 wt% or 0.1 wt% to 1 wt% or 2 wt% or 3 wt%, based on the total weight of the composition.
Packaging film
The composition is formed into an encapsulating film. Compositions such as the compositions described in any of the above embodiments or combinations of two or more embodiments are used to form an encapsulating film.
In one embodiment, the composition forms the entire encapsulation film.
(A) The non-polar ethylenic polymer, (B) the organic peroxide, (C) the silane coupling agent, (D) the coagent, and any optional additive may be added to each other and compounded with each other in any order or simultaneously. In one embodiment, the organic peroxide, silane coupling agent, coagent, and any optional additives are pre-mixed, and the pre-mixture is added to the non-polar ethylenic polymer prior to or during compounding. In one embodiment, dry pellets of the non-polar ethylenic polymer are soaked in a pre-mix, and the soaked pellets are then compounded.
Non-limiting examples of suitable compounding equipment include internal batch mixers (e.g., BANBURY and bold internal mixers) and continuous single or twin screw mixers (e.g., FARREL continuous mixers, BRABENDER single screw mixers, WERNER and PFLEIDERER twin screw mixers, and bus kneading continuous extruders). The type of mixer used and the operating conditions of the mixer may affect the properties of the composition such as viscosity, volume resistivity and smoothness of the extruded surface.
In one embodiment, it is desirable to avoid or limit crosslinking until lamination. Premature crosslinking and/or premature decomposition of the organic peroxide may result in a reduction in the glass adhesion of the encapsulation film. In other words, the encapsulating film remains reactive until lamination, at which point crosslinking is complete, and the encapsulating film composition of the encapsulating film becomes a reaction product that includes the non-polar ethylenic polymer, the silane coupling agent, and the coagent, and contains little, if any, residual organic peroxide. Therefore, the compounding temperature of the composition is lower than the decomposition temperature of the organic peroxide. In one embodiment, the compounding temperature of the composition is from 80 ℃ or 90 ℃ to 100 ℃ or 110 ℃ or 120 ℃.
Packaging film 1: in one embodiment, the encapsulating film is comprised of a composition comprising: (A) a non-polar ethylenic polymer having a density of 0.850g/cc to 0.890g/cc, (B) an organic peroxide, (C) a silane coupling agent, and (D) an auxiliary agent comprising triallyl phosphate.
And (3) packaging film 2: in one embodiment, the encapsulating film is comprised of a composition comprising: (A) from 50 wt% or 80 wt% or 95 wt% to 98.5 wt% or 98.75 wt% or 99 wt% or 99.5 wt% or less than 100 wt%, based on the total weight of the composition, of a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890 g/cc; (B) from 0.1 wt% or 0.5 wt% or 0.75 wt% to 1.5 wt% or 2 wt% or 3 wt% or 5 wt% of an organic peroxide, based on the total weight of the composition; (C) 0.01 wt% or 0.05 wt% or 0.1 wt% or 0.2 wt% to 0.3 wt% or 0.5 wt% or 1 wt% or 2 wt% of a silane coupling agent, based on the total weight of the composition; (D) 0.01 wt% or 0.1 wt% or 0.2 wt% to 1.0 wt% or 1.3 wt% or 1.5 wt% adjuvant based on the total weight of the composition. It is understood that the total amount of components (a), (B), (C), (D) and any optional additives is 100 wt% of the composition.
And (3) packaging film: in one embodiment, the encapsulating film is comprised of a composition comprising: (A) from 95 wt% to 99 wt%, based on the total weight of the composition, of a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890 g/cc; (B) 0.75 wt% to 1.5 wt% of an organic peroxide, based on the total weight of the composition; (C) 0.1 wt% to 0.3 wt%, based on the total weight of the composition, of a silane coupling agent; (D) 0.2 wt% to 1.3 wt% of an adjuvant, based on the total weight of the composition. It is understood that the total amount of components (a), (B), (C), (D) and any optional additives is 100 wt% of the composition.
In one embodiment, the encapsulation film is based on a volume resistivity at 60 ℃ of greater than or equal to 2.0 x 10 15 ohm. cm or 2.1X 10 15 ohm. cm or 2.2X 10 15 ohm. cm or 2.5X 10 15 ohm. cm or 3.0X 10 15 ohm. cm or 4.0X 10 15 ohm. cm or 5.0X 10 15 ohm. cm or 6.0X 10 15 ohm. cm or 7.0X 10 15 ohm. cm or 8.0X 10 15 ohm. cm or 9.0X 10 15 ohm. cm to 9.5 x 10 15 ohm. cm or 1.0X 10 16 ohm. cm or 1.2X 10 16 ohm. cm or 1.4X 10 16 ohm. cm or 1.5X 10 16 ohm. cm of encapsulation film 1, encapsulation film 2, or encapsulation film 3.
In one embodiment, the encapsulation film is based on a volume resistivity at 60 ℃ of greater than or equal to 2.1 x 10 15 ohm. cm to 1.0 x 10 16 ohm. cm of encapsulation film 1, encapsulation film 2, or encapsulation film 3.
In one embodiment, the thickness of the encapsulation film is 0.25mm or 0.275mm or 0.3mm or 0.325mm or 0.35mm or 0.375mm or 0.4mm to 0.425mm or 0.45mm or 0.475mm or 0.5mm or 0.525mm or 0.55 mm.
In one embodiment, the encapsulating film is a layer wherein a single layer is comprised of the composition of the present invention. In one embodiment, the encapsulating film has two or more layers, wherein at least one layer is comprised of the composition of the present invention.
Electronic device
The compositions of the present disclosure are useful in the construction of electronic device modules, and in particular, encapsulation films are useful in the construction of electronic device modules. The encapsulating film serves as one or more "shells" of the electronic device, i.e., is applied to one or both surfaces of the electronic device, e.g., as a front encapsulating film or a back encapsulating film, or as both a front encapsulating film and a back encapsulating film, e.g., where the device is fully encapsulated within a material.
In one embodiment, an electronic device module comprises (i) at least one electronic device, a plurality of such devices typically arranged in a linear or planar pattern; (ii) at least one cover plate; and (iii) at least one encapsulating film at least partially comprised of the composition of the present disclosure. The encapsulation film is interposed between the cover plate and the electronic device, and the encapsulation film exhibits good adhesion to both the electronic device and the cover plate.
In one embodiment, an electronic device module comprises (i) at least one electronic device, a plurality of such devices typically arranged in a linear or planar pattern; (ii) a front cover plate; (iii) a front encapsulation film; (iv) a rear packaging film; and (v) a backsheet, wherein at least one of (iii) the front encapsulant film and (iv) the back encapsulant film is at least partially comprised of a composition of the present disclosure. The electronic device is sandwiched between the front and back encapsulant films, wherein the cover and back sheets encapsulate the front encapsulant film/electronic device/back encapsulant film unit.
In one embodiment, the cover plate is glass, acrylic, polycarbonate, polyester, or a fluorine-containing resin. In another embodiment, the cover plate is glass.
In one embodiment, the back sheet is a single or multi-layer film composed of glass, metal, or polymer resin. The back sheet is a film composed of glass or polymer resin. In another embodiment, the backsheet is a multilayer film comprised of a fluoropolymer layer and a polyethylene terephthalate layer.
In one embodiment, the electronic device is a solar cell or a Photovoltaic (PV) cell.
In one embodiment, the electronics module is a PV module.
Fig. 1 illustrates an exemplary PV module. The rigid PV module 10 comprises photovoltaic cells 11(PV cells 11) surrounded or encapsulated by a front encapsulant film 12a and a rear encapsulant film 12 b. The glass cover plate 13 covers the front surface of the portion of the front encapsulant film 12a disposed over the PV cells 11. A back sheet 14, such as a second glass cover sheet or a polymer substrate, supports the rear surface of the portion of the rear encapsulant film 12b disposed on the rear surface of the PV cell 11. Backsheet 14 need not be transparent if the surface of the PV cells opposite backsheet 14 do not react to sunlight. In this embodiment, the encapsulating films 12a and 12b completely encapsulate the PV cells 11. In the embodiment shown in fig. 1, the front encapsulation film 12a directly contacts the glass cover plate 13, and the rear encapsulation film 12b directly contacts the back plate 14. The PV cell 11 is sandwiched between the front and rear encapsulant films 12a, 12b such that both the front and rear encapsulant films 12a, 12b are in direct contact with the PV cell 11. The front and rear encapsulant films 12a, 12b are also in direct contact with each other in locations where there are no PV cells 11.
The encapsulation film of the present disclosure may be a front encapsulation film, a rear encapsulation film, or both a front encapsulation film and a rear encapsulation film. In one embodiment, the encapsulation film of the present disclosure is a front encapsulation film. In another embodiment, the encapsulation film is both a front encapsulation film and a back encapsulation film.
In one embodiment, an encapsulation film comprising the composition of the present disclosure is applied to an electronic device by one or more lamination techniques. The cover sheet is brought into direct contact with the first surface of the encapsulation film and the electronic device is brought into direct contact with the second surface of the encapsulation film by lamination. The cover plate is brought into direct contact with the first surface of the front encapsulation film, the back plate is brought into direct contact with the second surface of the rear encapsulation film, and the electronic device is fixed between and in direct contact with the second surface of the front encapsulation film and the first surface of the rear encapsulation film.
In one embodiment, the lamination temperature is sufficient to activate the organic peroxide and crosslink the composition, i.e., the composition comprising the non-polar ethylenic polymer, the organic peroxide, the silane coupling agent, and the coagent remains reactive until lamination occurs when crosslinking occurs. During crosslinking, the silane coupling agent forms a chemical bond between two or more of the molecular chains of the non-polar ethylenic polymer through a silane bond. "silane bonds" have the structure-Si-O-Si-. Each silane linkage may link two or more or three or more molecular chains of the non-polar ethylenic polymer. The silane coupling agent also interacts with the surface of the cover plate to increase the adhesion between the encapsulation film and the cover plate. After lamination, the composition is the reaction product of a non-polar ethylenic polymer, an organic peroxide, a silane coupling agent, and an adjuvant.
In one embodiment, the lamination temperature for producing the electronic device is 130 ℃ or 135 ℃ or 140 ℃ or 145 ℃ to 150 ℃ or 155 ℃ or 160 ℃. In one embodiment, the lamination time is 8 minutes or 10 minutes or 12 minutes or 15 minutes to 18 minutes or 20 minutes or 22 minutes or 25 minutes.
In one embodiment, an electronic device of the present disclosure includes an encapsulating film comprised of a composition that is the reaction product of: (A) a non-polar ethylenic polymer, (B) an organic peroxide, (C) a silane coupling agent, and (D) an auxiliary agent comprising triallyl phosphate, and the initial glass adhesion of the encapsulating film is greater than 120N/cm or 130N/cm or 140N/cm or 150N/cm or 160N/cm or 170N/cm to 180N/cm or 190N/cm or 195N/C or 200N/cm.
In one embodiment, the electronic device of the present disclosure includes an encapsulation film according to encapsulation film 1, encapsulation film 2, or encapsulation film 3 having one, some, or all of the following properties:
(i) an initial glass adhesion force of greater than 120N/cm or 130N/cm or 140N/cm or 150N/cm or 160N/cm or 170N/cm to 180N/cm or 190N/cm or 195N/cm or 200N/cm; and/or
(ii) A volume resistivity at 60 ℃ of 2.0X 10 or more 15 ohm. cm or 2.1X 10 15 ohm. cm or 2.2X 10 15 ohm. cm or 2.5X 10 15 ohm. cm or 3.0X 10 15 ohm. cm or 4.0X 10 15 ohm. cm or 5.0X 10 15 ohm. cm or 6.0X 10 15 ohm. cm or 7.0X 10 15 ohm. cm or 8.0X 10 15 ohm. cm or 9.0X 10 15 ohm. cm to 9.5 x 10 15 ohm. cm or 1.0X 10 16 ohm. cm or 1.2X 10 16 ohm. cm or 1.4X 10 16 ohm. cm or 1.5X 10 16 ohm.cm。
In one embodiment, the electronic device of the present disclosure includes an encapsulation film according to encapsulation film 1, encapsulation film 2, or encapsulation film 3 having both properties (i) and (ii).
In one embodiment, the electronic device of the present disclosure includes an encapsulation film according to encapsulation film 1, encapsulation film 2, or encapsulation film 3 having one, some, or all of the following properties:
(i) an initial glass adhesion greater than 140N/cm to 190N/cm; and/or
(ii) A volume resistivity at 60 ℃ of 2.1X 10 or more 15 Cm to 1.0X 10 16 ohm.cm。
In one embodiment, the electronic device of the present disclosure includes an encapsulation film according to encapsulation film 1, encapsulation film 2, or encapsulation film 3 having both properties (i) and (ii).
Some embodiments of the disclosure will now be described in detail in the following examples.
Examples of the invention
Material
EVA: ethylene/vinyl acetate copolymer having a density of 0.955g/cc (measured in accordance with ASTM D792), a Melt Index (MI) of 6.0g/10min (measured in accordance with ASTM D1238 at 190 ℃, 2.16 kg), and a vinyl acetate content of 28 wt%, based on the total weight of the copolymer, obtainable from DuPont (DuPont) as Elvax 260
POE: ethylene/octene copolymer (non-polar ethylene based Polymer), density 0.880g/cc and MI 18.0g/10min
Peroxide: 2-ethylhexyl tert-butylperoxy carbonate (organic peroxide available from Acoma)
VMMS: 3- (trimethoxysilyl) propyl methacrylate (a silane coupling agent available from Dow Corning)
TAIC: triallyl isocyanurate (a crosslinking aid available from fangruda Chemicals co., ltd.)
TAP: triallyl phosphate (a crosslinking aid available from Tokyo Chemical Industry Co., Ltd. (TCI Chemical Industry Co., Ltd.))
Sample preparation
The compositions were prepared according to table 1 below by first pre-mixing the organic peroxide, silane coupling agent and coagent in a glass jar at the desired percentages set forth in table 1. Depending on the example (see table 1), dry polymer pellets of EVA or POE were placed into the tank. To ensure that the cure package (i.e., organic peroxide, silane coupling agent, and coagent) is evenly distributed and completely immersed in the pellets, the jar is placed into a 40 ℃ oven and periodically agitated every 15 minutes.
The composition was compression molded into a 0.5mm film. Compression molding was performed using a hydraulic press. The composition was preheated at 120 ℃ for 5 minutes without applied pressure, followed by 2 stages of applied pressure. Stage 1 was a pressure of 5MPa for 0.5 min. Stage 2 was a pressure of 10MPa for 0.5 min. Subsequently, the temperature was raised to 150 ℃ and kept at a pressure of 10MPa for 15 minutes. Finally, the temperature was allowed to cool to room temperature and the pressure was released.
For the volume resistivity test, each compression molded film was cut into four replicates to be tested.
TABLE 1
Figure BDA0002290817690000171
CE-comparative example
IE-an example of the invention
CE1-4 is based on EVA films. These comparative examples show that when TAIC (CE3) or TAP (CE4) is used as an adjuvant in EVA-based films, some VR improvement is seen in EVA-based compositions, but the initial glass adhesion remains low (113N/cm and 117N/cm for CE3 and CE4, respectively).
CE5-7 and IE1-3 used non-polar vinyl polymer films. Comparison of IE1-3 with CE5-6 shows that the inclusion of TAP in a non-polar ethylenic polymer film results in VR improvement. Specifically, the examples show that VR increases by about 4.7-20 x when cured with TAP compared to the base resin alone (CE 5). Volume resistivity at 60 ℃ of IE1-IE3 was 4.9X 10, respectively 15 ohm.cm、9.5×10 15 Cm and 2.2X 10 15 ohm. cm, while the volume resistivity of CE5 (non-polar ethylene-based polymer alone) at 60 ℃ is 4.7X 10 14 ohm.cm。
Comparison of IE1 and IE3 with CE7 (non-polar vinyl polymer with TAIC) also shows that in addition to the improvement in VR compared to the base resin alone, the use of TAP as an aid also results in an improvement in initial glass adhesion while maintaining the VR improvement.Specifically, VR for IE1 is 4.9X 10 15 And the initial glass adhesion was 167N/cm, while the VR for CE7 was 2.0X 10 15 And the initial glass adhesion was 135N/cm.
It is specifically intended that the present disclosure not be limited to the embodiments and illustrations contained herein, but include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims.

Claims (14)

1. An encapsulating film comprising a composition comprising:
(A) from 50 wt% to 99 wt%, based on the total weight of the composition, of a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890g/cc, wherein the non-polar ethylenic polymer is an ethylene/a-olefin copolymer;
(B) 0.1 wt% to 5 wt% of an organic peroxide, based on the total weight of the composition;
(C) 0.01 to 2 wt% of a silane coupling agent, based on the total weight of the composition; and
(D) 0.01 to 1.5 wt% of an adjuvant comprising triallyl phosphate, based on the total weight of the composition.
2. The encapsulation film of claim 1, wherein the alpha-olefin from which the ethylene/alpha-olefin copolymer is made is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-dodecene, and mixtures of two or more of these monomers.
3. The encapsulation film of claim 2, wherein the non-polar ethylenic polymer is selected from the group consisting of ethylene/a-olefin random copolymers and ethylene/a-olefin block copolymers.
4. The encapsulating film according to any one of claims 1 to 3, wherein the composition consists of:
(A) 95 to 99 weight percent of the non-polar ethylenic polymer, based on the total weight of the composition;
(B) 0.75 wt% to 1.5 wt% of the organic peroxide, based on the total weight of the composition;
(C) 0.1 to 0.3 wt%, based on the total weight of the composition, of the silane coupling agent; and
(D) 0.2 to 1.3 wt% of the adjuvant, based on the total weight of the composition.
5. The encapsulating film of claim 4, wherein the adjuvant is present in an amount of 0.2 wt% to 1.0 wt% based on the total weight of the composition.
6. The encapsulation film of any one of claims 1 to 3, wherein the coagent comprises triallyl phosphate and at least one other compound.
7. The encapsulating film according to any one of claims 1 to 3, wherein the coagent comprises from more than 20 wt% to less than 100 wt% triallyl phosphate, based on the total weight of the coagent.
8. The encapsulating film of any one of claims 1 to 3, wherein the auxiliary agent comprises a mixture of triallyl phosphate and at least one of (i) triallyl cyanurate and triallyl isocyanurate.
9. The encapsulating film of claim 8, wherein the adjuvant comprises 50 wt% to less than 100 wt% triallyl phosphate, based on the total weight of the adjuvant.
10. The encapsulation film of any one of claims 1 to 3, having a volume resistivity at 60 ℃ of greater than or equal to 2.1 x 10 15 Cm to 1.0X 10 16 ohm.cm。
11. An electronic device module, comprising:
an electronic device, and
at least one membrane comprised of a crosslinked polymeric composition that is the reaction product of a composition comprising:
(A) from 50 wt% to 99 wt%, based on the total weight of the composition, of a non-polar ethylenic polymer having a density from 0.850g/cc to 0.890g/cc, wherein the non-polar ethylenic polymer is an ethylene/a-olefin copolymer;
(B) 0.1 wt% to 5 wt% of an organic peroxide, based on the total weight of the composition;
(C) 0.01 to 2 wt% of a silane coupling agent, based on the total weight of the composition; and
(D) 0.01 to 1.5 wt% of an adjuvant comprising triallyl phosphate, based on the total weight of the composition.
12. The electronic device module of claim 11, wherein the at least one film has a volume resistivity at 60 ℃ of greater than or equal to 2.1 x 10 15 Cm to 1.0X 10 16 ohm.cm。
13. The electronic device module of claim 11 or 12, wherein the crosslinked polymer composition is the reaction product of:
(A) 95 to 99wt of the non-polar ethylene-based polymer, based on the total weight of the composition;
(B) 0.75 wt% to 1.5 wt% of an organic peroxide, based on the total weight of the composition;
(C) 0.1 to 0.3 wt%, based on the total weight of the composition, of the silane coupling agent; and
(D) 0.2 to 1.3 wt% of the triallyl phosphate-containing adjuvant, based on the total weight of the composition,
wherein the at least one film has a volume resistivity at 60 ℃ of greater than or equal to 2.2 x 10 15 Cm to 9.5X 10 15 ohm.cm。
14. The electronic device module of claim 11 or 12, wherein the electronic device is a photovoltaic cell.
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